# US 8,541,521 B2 · Catalyst compounds and use thereof

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- Number: US 8,541,521 B2
- Document ID: US8541521B2
- Status: Granted
- Kind: B2
- Application number: 12/908,257
- Filed: 2010-10-20
- Published: 2011-04-28
- Granted: 2013-09-24
- Earliest claimed: 2009-10-28
- Assignees: ExxonMobil Chemical Patents Inc.
- Applicants: Garth R. Giesbrecht; Timothy M. Boller; Alexander Z. Voskoboynikov; Andrey F. Asachenko; Mikhail V. Nikulin; Alexey A. Tsarev
- Inventors: Garth R. Giesbrecht; Timothy M. Boller; Alexander Z. Voskoboynikov; Andrey F. Asachenko; Mikhail V. Nikulin; Alexey A. Tsarev
- Web page: https://patentgrep.com/patent/US8541521B2

## CPC

- C07F 7/00: Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)

## Abstract

Group 4 catalyst compounds containing di-anionic tridentate nitrogen/oxygen based ligands are provided. The catalyst compounds are useful, with or without activators, to polymerize olefins, particularly α-olefins, or other unsaturated monomers. Systems and processes to oligomerize and/or polymerize one or more unsaturated monomers using the catalyst compound, as well as the oligomers and/or polymers produced therefrom are also provided.

## Claims

### Claim 1

A transition metal catalyst compound represented by one of the structures:
wherein
each X is, independently, a hydride, a halogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl;
w is 0, 1, 2 or 3;
each R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 and R11 is, independently, a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, a substituted halocarbyl, a halogen, an alkoxide, a sulfide, an amide, a phosphide, a silyl or an anionic heteroatom-containing group, or independently, may join together to form a C4 to C62 cyclic or polycyclic ring structure;
L is a neutral ligand bonded to M;
M is Hf, Zr or Ti;
m is 0, 1 or 2 and indicates the absence or presence of L; and
n is 1 or 2.

### Claim 2 (depends on 1)

The compound of claim 1, wherein the structure is F.

### Claim 3 (depends on 1)

The compound of claim 1, wherein n is 1 and w is 3.

### Claim 4 (depends on 1)

The compound of claim 1, wherein R5 is methyl or phenyl for structures B, D, E or F and R6 is methyl for structure A.

### Claim 5 (depends on 1)

The compound according to claim 1, wherein n is 1 and the structure is:
wherein Me is methyl and w is 3.

### Claim 6 (depends on 5)

The compound of claim 5, wherein when R1 is a hydrogen atom for structure A1, M may react with the R1 hydrogen atom to generate HX and a bond is formed between the carbon bearing position at R1 and M or when R6 is a hydrogen atom for structure B1, D1, or E1, M may react with the R6 hydrogen atom to generate HX and a bond is formed between the carbon bearing position at R6 and M.

### Claim 7 (depends on 1)

The compound of claim 1, wherein at least one of R6 or R11 is not a hydrogen atom for A; or for B, C, D, E, or F, at least one of R5 or R11 is not a hydrogen atom.

### Claim 8 (depends on 1)

The compound of claim 1, wherein at least one of R6 or R11 is not a hydrogen atom for A; or for B, C, D, E, or F, at least one of R5 or R11 is not a hydrogen atom; and w is 3.

### Claim 9 (depends on 1)

The compound of claim 1, wherein when R1 is a hydrogen atom for structure A, M may react with the R1 hydrogen atom to generate HX and a bond is formed between the carbon bearing position at R1 and M or when R6 is a hydrogen atom for structure B, D, or E, M may react with the R6 hydrogen atom to generate HX and a bond is formed between the carbon bearing position at R6 and M.

### Claim 10 (depends on 1)

The compound of claim 1, wherein the neutral ligand L includes molecules of pyridine, acetonitrile, diethyl ether, tetrahydrofuran, dimethylaniline, trimethylamine, tributylamine, trimethylphosphine, triphenylphosphine, lithium chloride, ethylene, propylene, butene, octene, or styrene.

### Claim 11

A transition metal catalyst composition represented by one of the structures:
wherein
each X is, independently, a hydride, a halogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl;
w is 0, 1, 2 or 3;
each R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 and R11 is, independently, a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, a substituted halocarbyl, a halogen, an alkoxide, a sulfide, an amide, a phosphide, a silyl or an another anionic heteroatom-containing group, or independently, may join together to form a C4 to C62 cyclic or polycyclic ring structure;
L is a neutral ligand bonded to M;
M is Hf, Zr or Ti;
m is 0, 1 or 2 and indicates the absence or presence of L;
n is 1 or 2;
Me is methyl; and
an activator.

### Claim 12 (depends on 11)

The composition according to claim 11, wherein the structure is F.

### Claim 13 (depends on 11)

The composition of claim 11, wherein n is 1 and w is 3.

### Claim 14 (depends on 11)

The composition of claim 11, wherein R5 is methyl or phenyl for structures B, D, E or F and R6 is methyl for structure A.

### Claim 15 (depends on 11)

The composition according to claim 11, wherein n is 1 and the structure is:
wherein Me is methyl and w is 3.

### Claim 16 (depends on 11)

The composition of claim 11, wherein at least one of R6 or R11 is not a hydrogen atom for A; or for B, C, D, E, or F, at least one of R5 or R11 is not a hydrogen atom; and w is 3.

### Claim 17 (depends on 6)

The composition of claim 6, wherein when R1 is a hydrogen atom for structure A, M may react with the R1 hydrogen atom to generate HX and a bond is formed between the carbon bearing position at R1 and M or when R6 is a hydrogen atom for structure B, D, or E, M may react with the R6 hydrogen atom to generate HX and a bond is formed between the carbon bearing position at R6 and M.

### Claim 18 (depends on 11)

The composition of claim 11, wherein the neutral ligand L includes molecules of pyridine, acetonitrile, diethyl ether, tetrahydrofuran, dimethylaniline, trimethylamine, tributylamine, trimethylphosphine, triphenylphosphine, lithium chloride, ethylene, propylene, butene, octene, or styrene.

### Claim 19

A process for polymerization comprising:
contacting ethylene and, optionally, one or more unsaturated monomers with a transition metal catalyst compound represented by one of the structures:
wherein
each X is, independently, a hydride, a halogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl;
w is 0, 1, 2 or 3;
each R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 and R11 is, independently, a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, a substituted halocarbyl, a halogen, an alkoxide, a sulfide, an amide, a phosphide, a silyl or an anionic heteroatom-containing group, or independently, may join together to form a C4 to C62 cyclic or polycyclic ring structure;
L is a neutral ligand bonded to M;
M is Hf, Zr or Ti;
m is 0, 1 or 2 and indicates the absence or presence of L;
Me is methyl; and
n is 1 or 2.

### Claim 20 (depends on 19)

The process of claim 19, wherein the structure is A.

### Claim 21 (depends on 19)

The process of claim 19, wherein n is 1 and w is 3.

### Claim 22 (depends on 19)

The process of claim 19, wherein R5 is methyl or phenyl for structures B, D, E or F and R6 is methyl for structure A.

### Claim 23 (depends on 19)

The process according to claim 19, wherein n is 1 and the structure is:
wherein Me is methyl and w is 3.

### Claim 24 (depends on 19)

The process of claim 19, wherein the neutral ligand L includes molecules of pyridine, acetonitrile, diethyl ether, tetrahydrofuran, dimethylaniline, trimethylamine, tributylamine, trimethylphosphine, triphenylphosphine, lithium chloride, ethylene, propylene, butene, octene, or styrene.

### Claim 25

A process for polymerization comprising:
contacting ethylene and, optionally, one or more unsaturated monomers with a transition metal catalyst composition represented by one of the structures:
wherein
each X is, independently, a hydride, a halogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl;
w is 0, 1, 2 or 3;
each R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 and R11 is, independently, a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, a substituted halocarbyl, a halogen, an alkoxide, a sulfide, an amide, a phosphide, a silyl or an another anionic heteroatom-containing group, or independently, may join together to form a C4 to C62 cyclic or polycyclic ring structure;
L is a neutral ligand bonded to M;
M is Hf, Zr or Ti;
m is 0, 1 or 2 and indicates the absence or presence of L;
n is 1 or 2;
Me is methyl; and
an activator.

### Claim 26 (depends on 25)

The process of claim 25, wherein the structure is A.

### Claim 27 (depends on 25)

The process of claim 25, wherein n is 1 and w is 3.

### Claim 28 (depends on 25)

The process of claim 25, wherein R5 is methyl or phenyl for structures B, D, E or F and R6 is methyl for structure A.

### Claim 29 (depends on 25)

The process according to claim 25, wherein n is 1 and the structure is:
wherein Me is methyl and w is 3.

### Claim 30 (depends on 25)

The process of claim 25, wherein the neutral ligand L includes molecules of pyridine, acetonitrile, diethyl ether, tetrahydrofuran, dimethylaniline, trimethylamine, tributylamine, trimethylphosphine, triphenylphosphine, lithium chloride, ethylene, propylene, butene, octene, or styrene.

### Claim 31 (depends on 25)

The process according claim 25, wherein the product of the polymerization process is homopolyethylene.